Metal complexes of bis-hydrazones

ABSTRACT

Bis-hydrazone metal complexes of the formula ##STR1## wherein A denotes an isocyclic or heterocyclic radical, R denotes a H atom, an alkyl group or an aryl radical, M denotes a divalent transition metal and zinc or cadmium, X 1  and X 2  independently of one another represent alkyl, cycloalkyl, aralkyl or aryl radicals, or conjointly form a fused carbocyclic or heterocyclic aromatic ring, L denotes a ligand having one or more coordinating N or S atoms, and n denotes the number 1 - 5, are useful for coloring plastic and lacquers in fast yellow to red shades.

The present invention relates to new metal complexes of bis-hydrazonesof the formula ##STR2## wherein A denotes an isocyclic or heterocyclicradical, R denotes a H atom, an alkyl group or an aryl radical, Mdenotes a divalent transition metal and zinc or cadmium, X₁ and X₂independently of one another represent alkyl, cycloalkyl, aralkyl oraryl radicals, or conjointly form a fused carbocyclic or heterocyclicaromatic ring, L denotes a ligand having one or more coordinating N or Satoms, and n denotes the number 1 - 5.

Preferred bis-hydrazone metal complexes are those of the formula##STR3## wherein A, L, R and M have the meaning indicated, X₃ denotes aH or halogen atom, an alkoxy or arylmercapto group containing 1 - 6 Catoms, an aralkoxy group having an alkyl radical of 1 - 4 C atoms, anaryloxy group, a nitro, carboxyl or carbamoyl group, alkylcarbamoyl oralkanoylamino group containing 2 - 6 C atoms or an arylcarbamoyl group,X₄ denotes a H or halogen atom, X₅ denotes a H or halogen atom, analkoxy or alkylmercapto group containing 1 - 6 C atoms, an aralkoxygroup having an alkyl radical of 1 - 4 C atoms, or an aryloxy group andX₆ denotes a H or halogen atom, a nitro, carboxyl or carbamoyl group, analkylcarbamoyl or alkanoylamino group containing 2 - 6 C atoms, or anarylcarbamoyl group and m denotes the number 1 - 3.

Compounds of particular interest are those of the formula ##STR4##wherein A, R, X₃ -X₆ and M have the meaning indicated and R' denotes ahydrogen atom, an OH group, an aliphatic or cycloaliphatic radical or anaromatic radical which is preferably free from stronglyelectron-attracting groups, or an amino, alkylamino, arylamino, acyl oracylamino group or a group of the formula ##STR5## wherein R₂ and R₃denote H atoms or alkyl or aryl groups and R"' denotes a H atom or anamino, alkyl or phenyl group.

Preferred metal complexes are also those of the formula ##STR6## whereinA, R, M, X₃ - X₆ have the meaning indicated and B, conjointly with the Natom, forms a heterocyclic ring system, preferably a pyridine ring.

Preferred metal complexes are also those of the formula ##STR7## whereinA, R, M, X₃ - X₆ have the meaning indicated and B₁ is an alkylene groupcontaining 2 - 10 C atoms, or an arylene group.

In the metal complexes of the formula indicated, M denotes, for example,a Co² ⁺ or Zn² ⁺ atom but preferably denotes a Cu² ⁺ atom and inparticular a Ni² ⁺ atom.

In the formulae indicated X₄ and X₆ perferably represent H or chlorineatoms, and X₃ and X₅ preferably represent H or chlorine atoms or alkoxygroups containing 1 - 4 C atoms.

R preferably denotes a H atom, an alkyl group containing 1 - 4 C atoms,or a phenyl group.

In the formulae indicated, A preferably denotes a radical of the formula##STR8## wherein Y₁ and Y₂ denote H or halogen atoms, alkyl or alkoxygroups having 1 - 4 C atoms, or nitro groups.

Preferred metal complexes are also those of the formula indicatedwherein A denotes a radical of the formula ##STR9## wherein R₈ denotesan OH group, an alkyl group containing 1 - 4 C atoms, or a phenylradical which is optionally substituted by halogen atoms or alkyl oralkoxy groups containing 1 - 4 C atoms.

The new metal complexes are obtained if a bishydrazone of the formula##STR10## is treated, in the presence of a ligand L which has theabovementioned meaning, with agents which donate the divalent transitionmetals or zinc and cadmium.

The starting material is preferably a bis-hydrazone of the formula##STR11## wherein A, R and X₃ - X₆ have the abovementioned meaning.

In formula (VIII) A preferably represents a radical of the formula (VI)or (VII).

The bis-hydrazones of the formula (VIII) are obtained a) by condensing amono-hydrazone of the formula ##STR12## with a hydroxyaldehyde orhydroxyketone of the formula ##STR13## or b) by condensing a compound ofthe formula ##STR14## wherein V denotes a group of the formula ##STR15##wherein Z₁ denotes an imino or thio group and the Z₂ denote halogenatoms, alkoxy groups, particularly methoxy groups, of sec. amino groups,with a mono-hydrazone of the formula ##STR16## or c) by condensing amono-hydrazone of the formula (X) with an azomethine of the formula##STR17## wherein Ph denotes a phenyl radical which is optionallysubstituted by halogen atoms, alkyl or alkoxy groups, containing 1 - 4 Catoms, alkoxycarbonyl groups containing 2 - 6 C atoms or nitro ortrifluoromethyl groups, and, in the formulae (VIII), (IX) and (XI), Aand R have the meaning indicated and, in the formulae (VIII), (X) and(XII), X₁ and X₂ have the meaning indicated.

The hydrazones of the formula (X) are obtained by reacting hydrazinewith a compound of the formula (XII). The following should be mentionedas examples of compounds of the formula (XII):3-imino-4,5-dichloro-pyrrolinone, 3-imino-4,5-dimethyl-pyrrolinone,3-imino-4,5-dimethyl-pyrrolinone, 3-imino-4,5-dicyclohexyl-pyrrolinone,3-imino-4,5-diphenyl-pyrrolinone, 3-imino-isoindolinone,4,5,6,7-tetrachloro-3-imino-isoindolinone,5,6-dichloro-3-imino-isoindolinone,4,5,7-trichloro-6-methoxy-3-imino-isoinodlinone,4,5,7-trichloro-6-ethoxy-3-imino-isoindolinone,5,7-dichloro-4,6-dimethoxy-3-imino-isoinodolinone,5,7-dichloro-4,6-diphenoxy-3-imino-isoindolinone,4,5,7-trichloro-6-methylmercapto-3-imino-isoindolinone,4,5,7-trichloro-6-phenylmercapto-3-imino-isoindolinone,3-imino-4,5-benzo-isoindolinone,4,5,6,7-tetraphenoxy-3-imino-isoindolinone, 5- or6-methyl-3-imino-isoindolinone, 5- or 6-phenyl-3-imino-isoindolinone, 4-or 7-chloro-3-imino-isoindolinone, 5- or 6-chloro-3-imino-isoindolinone,4- or 7-nitro-3-imino-isoindolinone, 5- or6-nitro-3-imino-isoindolinone, 5- or 6-methoxy-3-imino-isoindolinone, 5-or 6-ethoxy-3-imino-isoindolinone, 5- or6-phenoxy-3-imino-isoindolinone, 5-or6-methylmercapto-3-imino-isoindolinone, 5- or6-methylsulphonyl-3-imino-isoindolinone, 5- or6-acetylamino-3-imino-isoindolinone,3-imino-4,7-dithia-4,5,6,7-tetrahydro-isoindolinone,3-imino-4,7-diaza-isoindolinone,3,3-dimethoxy-4,5,6,7-tetrachloro-isoindolinone,3,3-dimethoxy-4,5,6,7-tetrabromo-isoindolinone, 3,3,6-trimethoxy-4,5,7-trichloro-isoindolinone,3,3-dimethoxy-4,5,7-trichloro-6-butoxy-isoindolinone,3,3-dimethoxy-4,5,7-trichloro-6-phenoxy-isoindolinone,3,3-dimethoxy-4,5,7-trichloro-6-(p-chlorophenoxy)-iso-indolinone,3,3-dimethoxy-4,5,7-trichloro-6-(o-methylphenoxy)-iso-indolinone,3,3-dimethoxy-4,5,7-trichloro-6-methylmercapto-iso-indolinone,3,3,-dmethoxy-4,5,7-trichloro-6-ethylmercapto-isoindolinone and3,3,4,6-tetramethoxy-5,7-dichloro-isoindolinone.

The pyrrolinones and isoindolinones mentioned are known compounds.

In accordance with process a), the hydrazones of the formula (X) arecondensed with hydroxyaldehydes or hydroxyketones of the formula (XI).

Aldehydes and ketones of particular interest are those of the formula##STR18## wherein Y₁ and Y₂ have the meaning indicated, R" denotes a Hatom or a methyl group and Z denotes a NH group or an O atom, and, inparticular, the hydroxyquinolines of the formula ##STR19## wherein R",Y₁ and Y₂ have the meaning indicated.

Aldehydes and ketones of particular interest are also those of thefollowing formulae ##STR20## wherein R₉ denotes a cyano, carboxyl orcarbamoyl group and R"and R₈ have the meaning indicated above, oraldehydes and ketones of the formula ##STR21## wherein R" and R₉ havethe meaning indicated above, and also aldehydes or ketones of theformula ##STR22## wherein R₁₀ denotes a H atom or an alkyl or arylgroup, and wherein R", Y₁ and Y₂ have the meaning indicated above, oraldehydes and ketones of the formula ##STR23## wherein Y₃ denotes a Hatom or a carboxyl, carbamoyl, phenylcarbamoyl or alkoxycarbonyl groupcontaining 2 - 6 C atoms, and Y₄ denotes a H or halogen atom or amethoxy, nitro or cyano group, or pyrazolone-aldehydes orpyrazolone-ketones of the formula ##STR24## wherein R₁₁ denotes an alkylgroup containing 1 - 4 C atoms, an alkoxycarbonyl group containing 2 - 5C atoms, a carboxyl group, a carbamoyl group or a group of the formulawherein M₂ denotes a Ca, Sr, Ba or Mn atoms, and Y₅ and Y₆ denote H orhalogen atoms, alkyl or alkoxy groups containing 1 - 4 C atoms, nitro,acylamino, carbamoyl or sulphamoyl groups or groups of the formula##EQU1## wherein M₂ denotes a Ca, Sr, Ba or Mn atoms and R" has themeaning indicated above.

The following aldehydes or ketones should be mentioned as examples:

1.hydroxybenzaldehydes:

Salicylaldehyde, 4-chloro-2-hydroxybenzaldehyde,5-chloro-2-hydroxybenzaldehyde, 3-nitro-2-hydroybenzaldehyde,5-nitro-2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde,3,5-dibromo-2-hydroxybenzaldehyde, 5-phenylazo-2-hydroxybenzaldehyde,5-(2'-chloro-phenylazo)-hydroxybenzaldehyde,5-(2',5'-dichloro-phenylazo)-2-hydroxybenzaldehyde,5-(2'-methyl-phenylazo)-2-hydroxybenzaldehyde,5-(2'-methoxyphenylazo)-2-hydroybenzaldehyde,5-(2'-methoxy-4'-nitrophenylazo)-2-hydroxybenzaldehyde and5-(2'-methoxy-5'-carbamoyl-phenylazo)-2-hydroxybenzaldehyde.

2. Hydroxynaphthaldehydes: 2-Hydroxynaphthaldehyde,6-bromo-2-hydroxynapthaldehyde, 5-nitro-2-hydroxynaphthaldehyde,2-hydroxy-3-carboxynaphthaldehyde,2-hydroxy-3-methoxycarbonyl-naphthaldehyde,2-hydroxy-3-phenylcarbamoyl-naphthaldehyde,2-hydroxy-3-(4'-chlorophenylcarbamoyl)-naphthaldehyde,2-hydroxy-3-(4'-chloro-2'-methylphenylcarbamoyl)-naphthaldehyde,2-hydroxy-3-(2',5'-dimethoxy-3'-chloro-phenylcarbamoyl-naphthaldehyde,2-hydroxy-6-bromo-3-carboxynaphthaldehyde and2-hydroxy-6-bromo-3-phenylcarbamoylnaphthaldehyde.

3. Heterocyclic aldehydes and ketones:

2,6-Dihydroxy-4-methyl-5-cyano-3-pyridinealdehyde,2,6-dihydroxy-4-methyl-5-carboxy-3-pyridinealdehyde,2,6-dihydroxy-4-methyl-5-carbamoyl-3-pyridinealdehyde,2,4-dihydroxy-3-quinolinealdehyde,5-chloro-2,4-dihydroxy-3-quinolinealdehyde,6-chloro-2,4-dihydroxy-3-quinolinealdhyde,7-chloro-2,4-dihydroxy-3-quinolinealdehyde,8-chloro-2,4-dihydroxy-3-quinolinealdehyde,6,8-dichloro-2,4-dihydroxy-3-quinolinealdehyde,7,8-dichloro-2,4-dihydroxy-3-quinolinealdehyde,6-methyl-2,4-dihydroxy-3-quinolinealdehyde,7-methyl-2,4-dihydroxy-3-quinolinealdehyde,8-methyl-2,4-dihydroxy-3-quinolinealdehyde,6-chloro-8-methyl-2,4-dihydroxy-3-quinolinealdehyde,2,4-dihydroxy-3-acetyl-quinoline,2,4-dihydroxy-3-acetyl-6-methyl-quinoline,2,4-dihydroxy-3-acetyl-6-chloro-quinoline,2,4-dihydroxy-3-benzoyl-quinoline,2-methyl-4,6-dihydroxy-5-pyrimidinealdehyde,2-phenyl-4,6-dihydroxy-5-pyrimidinealdehyde,2,4,6-trihydroxy-5-pyrimidinealdehyde,2,4,6-trihydroxy-5-acetylpyrimidine, 4-hydroxy-3-quinaldinealdehyde,6-chloro-4-hydroxy-3-quinaldinealdehyde,6-methoxy-4-hydroxy-3-quinaldinealdehyde,3-hydroxy-isoquinolone-4-aldehydes and other aldehydes.4-hydroxycoumarin-3-aldehyde, 1-phenyl-3-methyl-4-formyl-5-pyrazolone,1-phenyl-3-carboxy-4-formyl-5-pyrazolone,1-phenyl-3-methoxycarbonyl-4-formyl-5-pyrazolone,1-phenyl-3-ethoxycarbonyl-4-formyl-5-pyrazolone,1-(2'-chlorophenyl)-3-methyl-4-formyl-5-pyrazolone,1-(4'-chlorophenyl)-3-methyl-4-formyl-5-pyrazolone,1-(2'-methylphenyl)-3-methyl-4-formyl-5-pyrazolone,1-(4'-methylphenyl)-3-methyl-4-formyl-5-pyrazolone and1-phenyl-3-carbamoyl-4-formyl-5-pyrazolone.

Instead of the aldehydes or ketones, it is also possible to use iminesthereof, particularly the phenylimines of the formula XIV (process c),which can be obtained by known methods.

The mono-hydrazones of the formula (XIII) required for process b) areobtained, for example, by reacting the corresponding hydroxyketones orhydroxyaldehydes with hydrazine. The condensation of the hydrazone withthe oxo compound or the isoindolinone is appropriately carried out inwater or an organic solvent at elevated temperature, preferably between50° C and the boiling point of the solvent used. The following examplesof solvents should be mentioned: water, alcohol, glacial acetic acid,dioxane, dimethylformamide, N-methylpyrrolidone, butyrolactone, glycolmonoethyl ether, ethylene glycol, carbitol, glycol monomethyl ether,xylene, chlorobenzene, o-dichlorobenzene, nitrobenzene or mixturesthereof.

Since the resulting azomethines are sparingly soluble in the solventsmentioned, they can be isolated easily by filtration. Impurities whichmay be present can be removed by washing.

In certain cases it is possible to dispense with the isolation of thebis-azomethine and to carry out the reaction of the components (X) and(XI) or (XII) and (XIII) respectively in the same vessel, in thepresence of the metal donor and the ligand L.

The process c) proves particulary advantageous for the manufacture ofmetal complexes of the formula (III) wherein R' deontes a phenylradical.

As metal donors, the salts of zinc, manganese, cobalt, iron, preferablycopper, and, in particular, nickel, should be mentioned. It ispreferable to use the formates or acetates of these metals.

Ligands L which can be used are those having one or more coordinating Nor S atoms.

N-containing ligands which can be used are preferably ammonia or primaryaliphatic, cycloaliphatic or aromatic amines or amines, as well assecondary and tertiary heterocyclic amines, the N atoms of which areconstituents of one or more rings.

Ligands of particular interest are those of the formula R'--NH₂ or##STR25## wherein R' and B have the abovementioned meaning.

It is possible to use the most diverse monoamines or polyamines, forexample alkylamines having 1 - 10 C atoms, dialkylamines having 2 - 12 Catoms, phenyalkylamines, the alkyl radical of which contains 1 - 4 Catoms, mono- or di-cycloalkylamines having 5 - 6 C atoms in thecycloalkyl radical, heterocyclic, aromatic and cycloaliphatic amines ormonoaminobenzenes.

Diamines which can be used are preferably those of the formula H₂ N--B₂--NH₂ wherein B₂ denotes an alkylene group containing 2 - 10 C atoms, ap-phenylene group or a group --Ph--X--Ph wherein X denotes a directbond, an O or S atom, a methylene or ethylene group or a group of theformula --NH--, --SO₂ -- or --CO-- or --N=N--, or heterocyclic diamines.

Other N-containing ligands which should be mentioned are hydroazine,alkylhydrazines having 1-6 C atoms, arylhydrazines and hydrazones,hydroxylamine, amidines and hydrazides, and preferred S-containingligands which should be mentioned are the mercaptans.

The following ligands should be mentioned as examples: Ammonia,methylamine, ethylamine, ethanolamine, methoxyethylamine, N-propylamine,isopropylamine, n-butylamine, n-hexylamine, cyclohexylamine,n-octylamine, n-decylamine, n-propylamine, di-(2'-aminoethyl))-amine,tri-(2'-aminoethyl)-amine, ethylenediamine, 1,3-propylenediamine,1,4-butylenediamine, 1,6-hexylenediamine, benzylamine, aniline,4-amino-4'-dimethylaminoazobenzene, 2-, 3- or 4-methylaniline,dimethylanilines, chloroaniline, 2,4, 3,4 or 2,5-dichloroaniline,3-trifluoromethylaniline, 2-, 3- or 4-methoxyaniline, 2-, 3- or4-ethoxyaniline, 4,4'-diamino-diphenyl oxide, 4,4'-diaminodiphenylsulphide, 4,4'-diamino-diphenylmethane, 4,4'-diamino-diphenyl-sulphone,4,4'-diamino-diphenyl-ketone, 4,4'-diamino-azobenzene,4'-amino-4'-dimethylamino-azobenzene,2,2'-dimethyl-4,4'-diaminoazobenzene,2,2'-dimethoxy-4,4'-diaminoazobenzene, tri-(4-aminophenyl)-amine,1,2,3,-tri-(4'-aminophenoxy)-propane,tetra-(4'-aminophenoxymethyl)-methane,1-(2'-amino-ethylamino)-anthraquinone,1-(4'-amino-phenylamino-anthraquinone, pyridine, picolines, lutidines,quinoline, isoquinoline, pyrrolidone, piperidine, piperazine,N-methyl-piperazine, morpholine, 2-amino-benzimidazole,2-amino-benzthiazole, diethylenediamine, triethylenediamine, guanidine,3-amino-benzoic acid amide, 3-amino-benzoic acid anilide, 3- or4-acetylamino-aniliner, 3- or 4-benzoylamino-aniline, hydrazine,methylhydrazine, phenylhydrazine, 1,3,5-trihydrazino-s-triazine,4-methylphenyl-hydrazine, acetaldehydehydrazone, benzaldehydehydrazone,acetonehydrazone, acetophenonehydrazone, cyclohexanonehydrazone,hydroxylamine, formamidine, formamide, dimethylformamide, acetamide,benzamide, acetohydrazide, benzhydrazide, semicarbazide and decanetriol.

The polyfunctional ligands can be reacted according to choice with oneor more mols of the bis-hydrazone metal complex. Among thepolyfunctional ligands, the diamines are preferred. The molar ratiobetween metal complex and diamine is appropriately chosen in such a waythat each amino group is linked to one metal atom.

The addition of the ligand can take place before or at the same time asthe addition of the metal ion.

The reaction of bis-hydrazones with the ligands and the metal donors isappropriately carried out at between 50° and 150° in an organic solvent,appropriately in one of the abovementioned solvents.

The new bis-hydrazone metal complexes are valuable pigments which can beused in a finely divided form for pigmenting high-molecular organicmaterial, for example cellulose ethers and esters, such asethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate,natural resins or synthetic resins, such as polymerisation resins orcondensation resins, for example aminoplasts, particularlyurea-formaldehyde and melamine-formaldehyde, alkyd resins, phenoplasts,polycarbonates, polyolefines, such as polystyrene, polyvinyl chloride,polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters,polyamides, polyurethanes or polyesters, rubber, casein, silicone andsilicone resins, on their own or as mixtures.

It is immaterial here whether the high molecular compounds mentioned arepresent as plastic compositions or melts or in the form of spinningsolutions, lacquers, paints or printing inks. Depending on theapplication, it proves advantageous to use the new pigments as toners orin the form of preparations.

The new pigments are distinguished by a surprisingly good heatstability, high tinctorial strength and pure shade and, very often, by asurprisingly increased insolubility.

In the examples which follow, unless otherwise specified, the partsdenotes parts by weight and the percentages denote percentages byweight.

EXAMPLE 1

1.32 parts of 2,4-dihydroxyquinoline-3-N-phenylaldimine and 1.50 partsof 4,5,6,7-tetrachloro-isoindolin-1-on- 3-ylidenehydrazine are stirredfor 10 minutes at 100° C in 75 parts by volume of methylcellosolve; themixture is reacted with 1.25 parts of nickel acetate tetrahydrate and iswarmed for a further 4 hours at 100° C. The reaction product is filteredoff while hot, rinsed with alcohol and acetone and dried at 80° C invacuo. This gives 2.67 parts (86% of theory) of a yellow pigment of theformula:

    ______________________________________                                         ##STR26##                                                                    Micro-analysis:                                                                 %       C        H       N      Cl     Ni                                   ______________________________________                                        calculated                                                                              46.49    2.11    11.29  22.87  9.46                                 found     45.8     2.2     11.5   22.8   9.2                                  ______________________________________                                    

EXAMPLE 2

2.35 parts of the bis-hydrazones (formed, for examples, from2,4-dihydroxyquinoline-3-aldehyde and4,5,6,7-tetrachloroisoindolin-1-on-3-ylidenehydrazine), 0.47 part byvolume of aniline and 1.25 parts of nickel acetate tetrahydrate arestirred for 3 hours at 100° C in 75 parts by volume of methylcellosolve.The thick mass is filtered at 85°-90° C and the product is washed withalcohol and acetone and dried, 2.75 parts (89% of theory) of the pigmentof the formula according to Example 1 being obtained.

    ______________________________________                                        Micro-analysis:                                                                 %       C        H       N      Cl     Ni                                   ______________________________________                                        calculated                                                                              46.49    2.11    11.29  22.87  9.46                                 found     46.5     2.1     11.4   22.7   9.5                                  ______________________________________                                    

The complexes of Examples 3 - 9 were prepared in accordance with Example1 and those of Examples 10 - 13 were prepared in accordance with Example2: ##STR27## wherein the symbols have the meaning indicated in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                                            Shade                                 Ex-                                     in                                    ample                                                                              Y.sub.1                                                                          Y.sub.2                                                                          Y.sub.3                                                                          Y.sub.4                                                                          X.sub.6                                                                          X.sub.5                                                                            X.sub.4                                                                          X.sub.3                                                                            M  Yield                                                                             PVC                                   __________________________________________________________________________    3    H  H  H  H  Cl OCH.sub.3                                                                          Cl Cl   Ni 91% yellow                                4    H  H  H  H  Cl OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Ni 87% yellow                                5    H  H  H  H  Cl OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cu 78% greenish-                                                                     tinged                                                                        yellow                                6    H  H  Cl H  Cl Cl   Cl Cl   Ni 88% yellow                                7    H  H  Cl H  Cl OCH.sub.3                                                                          Cl Cl   Ni 90% yellow                                8    H  H  Cl H  Cl OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Ni 87% yellow                                9    Cl Cl H  H  Cl OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Ni 90% yellow                                10   H  H  H  H  Cl OCH.sub.3                                                                          Cl Cl   Ni 88% yellow                                11   H  H  H  H  Cl OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Ni 93% yellow                                12   H  H  H  H  Cl OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cu 85% greenish-                                                                     tinged                                                                        yellow                                13   H  H  H  H  H  H    H  H    Ni 85% yellow                                __________________________________________________________________________

The metal complexes of formula A, which contain the ligand L instead ofaniline and which were prepared in accordance with Example 2, are shownin Examples 14-92 in Table 2. ##STR28##

                                      TABLE 2                                     __________________________________________________________________________    Ex-                                                     Shade in              ample                                                                             Y.sub.1                                                                          Y.sub.2                                                                          Y.sub.3                                                                          Y.sub.4                                                                          X.sub.3                                                                           X.sub.4                                                                          X.sub.5                                                                           X.sub.6                                                                          R  M  n    L          Yield                                                                             PVC                   __________________________________________________________________________    14  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 1 4-Chloroaniline                                                                             90% yellow                15  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 1 4-Methylaniline                                                                             89% yellow                16  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 1 4-Methoxyaniline                                                                            90% yellow                17  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 1 5-Aminobenzimidazole                                                                        94% yellow                18  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 1 Benzylamine   89% yellow                19  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 1 Cyclohexylamine                                                                             87% yellow                20  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 1 2,2,6,6-Tetramethyl-4                                                                       71% yellow                                                      aminopiperidine                         21  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 1 Pyridine      86% yellow                22  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 1 n-Octylamine  87% yellow                23  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 1 2-Ethanolamine                                                                              86% yellow                24  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 1 NH.sub.3      74% yellow                25  H  H  H  H  Cl  Cl Cl  Cl H  Ni 1 NH.sub.3      92% yellow                26  H  H  H  H  Cl  Cl Cl  Cl H  Ni 2 4,4'-Diaminodiphenyl-                                                                       92% yellow                                                      sulphone                                27  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 2 4,4'-Diaminodiphenyl-                                                                       86% yellow                                                      sulphone                                28  H  H  H  H  OCH.sub.3                                                                         Cl OCH.sub.3                                                                         Cl H  Ni 2 Hexamethylenediamine                                                                        96% yellow                29  H  H  H  H  Cl  Cl CH.sub.3 O                                                                        H  H  Ni 1 NH.sub.3      34.4%                                                                             yellow                30  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Zn 1 NH.sub.3      59.3%                                                                             yellow                31  H  H  H  H  Cl  Cl PhO Cl H  Ni 1 NH.sub.3      83.3%                                                                             yellow                32  H  H  H  H  H   H  H   H  H  Ni 1 NH.sub.3      90.0%                                                                             yellow                33  H  H  CH.sub.3                                                                         H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni 1 NH.sub.3      92.1%                                                                             yellow                34  H  H  CH.sub.3                                                                         H  Cl  Cl Cl  Cl H  Ni 1 NH.sub.3      79.5%                                                                             yellow-orange         35  H  H  Cl H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni 1 NH.sub.3      93.1%                                                                             yellow                36  H  H  Cl H  Cl  Cl Cl  Cl H  Ni 1 NH.sub.3      97.0%                                                                             yellow                37  H  H  H  H  Cl  Cl CH.sub.3 O                                                                        Cl CH.sub.3                                                                         Ni 1 NH.sub.3      83.3%                                                                             yellow-brown          38  H  H  H  H  H   H  H   H  CH.sub.3                                                                         Ni 1 NH.sub.3      91.2%                                                                             yellow                39  H  H  H  H  H   CH.sub.3                                                                         CH.sub.3 O                                                                        Cl H  Cu 1 NH.sub.3      81.5%                                                                             greenish-                                                                     tinged                                                                        yellow                40  H  H  H  H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni 1 Hydroxylamine 94.2%                                                                             yellow                41  H  H  H  H  Cl  Cl Cl  Cl H  Ni 1 Morpholine    85.6%                                                                             yellow                42  H  H  H  H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni 1 Benzylamine   93.6%                                                                             yellow                43  H  H  H  H  Cl  Cl PhO Cl H  Ni 1 Benzylamine   89.6%                                                                             yellow                44  H  H  H  H  Cl  Cl Cl  Cl H  Ni 1 Benzylamine   97.5%                                                                             yellow                45  H  H  H  H  H   H  H   H  H  Ni 1 Benzylamine   85.1%                                                                             yellow                46  H  H  CH.sub.3                                                                         H  Cl  Cl Cl  Cl H  Ni 1 Benzylamine   88.5%                                                                             yellow                47  H  H  Cl H  Cl  Cl Cl  Cl H  Ni 1 Benzylamine   77.2%                                                                             yellow                48  H  H  CH.sub.3                                                                         H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni 1 Benzylamine   87.5%                                                                             yellow                49  H  H  Cl H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni 1 Benzylamine   90.9%                                                                             yellow                50  H  H  H  H  Cl  Cl CH.sub.3 O                                                                        Cl CH.sub.3                                                                         Ni 1 Benzylamine   90.6%                                                                             yellow                51  H  H  H  H  H   H  H   H  CH.sub.3                                                                         Ni 1 Benzylamine   92.0%                                                                             yellow                52  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 1 NH.sub.2CHNH  89.3%                                                                             yellow                53  H  H  CH.sub.3                                                                         H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 1 Aniline       90.3%                                                                             yellow                54  H  H  CH.sub.3                                                                         H  Cl  Cl Cl  Cl H  Ni 1 Aniline       92.1%                                                                             yellow                55  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub. 3 O                                                                       Cl CH.sub.3                                                                         Ni 1 Aniline       80.6%                                                                             yellow                56  H  H  H  H  H   H  H   H  CH.sub.3                                                                         Ni 1 Aniline       84.6%                                                                             yellow                57  H  H  H  H  Cl  Cl Cl  Cl H  Ni 1 Pyridine      96.0%                                                                             yellow                58  H  H  H  H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni                                               Pyridine                                                                         96.0%                                                                            yellow                                                              59  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Cu 1 Pyridine      94.4%                                                                             greenish-                                                                     tinged                                                                        yellow                60  H  H  Cl H  Cl  Cl Cl  Cl H  Ni 1 Pyridine      91.5%                                                                             yellow                61  H  H  CH.sub.3                                                                         H  Cl  Cl Cl  Cl H  Ni 1 Pyridine      96.8%                                                                             yellow                62  H  H  H  H  Cl  Cl CH.sub.3 O                                                                        Cl CH.sub.3                                                                         Ni 1 Pyridine      90.3%                                                                             yellow-brown          63  H  H  H  H  H   H  H   H  CH.sub.3                                                                         Ni 1 Pyridine      83.3%                                                                             yellow                64  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 1 2-Quinoline   87.5%                                                                             yellow                65  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 1 Phenylhydrazine                                                                             93.0%                                                                             yellow                66  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 1 Benzhydrazide 90.0%                                                                             yellow                67  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 1 Decanethiol   88.6%                                                                             yellow-brown          68  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 2 Ethylenediamine                                                                             87.5%                                                                             yellow                69  H  H  CH.sub.3                                                                         H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni 2 Ethylenediamine                                                                             85.7%                                                                             yellow                70  H  H  CH.sub.3                                                                         H  Cl  Cl Cl  Cl H  Ni 2 Ethylenediamine                                                                             90.1%                                                                             yellow                71  H  H  Cl H  Cl  Cl Cl  Cl H  Ni 2 Ethylenediamine                                                                             82.1%                                                                             yellow                72  H  H  Cl H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni 2 Ethylenediamine                                                                             89.7%                                                                             yellow                73  H  H  H  H  H   H  H   H  CH.sub.3                                                                         Ni 2 Ethylenediamine                                                                             86.4%                                                                             yellow                74  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 2 Propylenediamine                                                                            92.9%                                                                             yellow                75  H  H  Cl H  Cl  Cl Cl  Cl H  Ni 2 Propylenediamine                                                                            86.2%                                                                             yellow                76  H  H  H  H  Cl  Cl Cl  Cl H  Ni 2 Hexamethylenediamine                                                                        93.1%                                                                             yellow                77  H  H  Cl H  Cl  Cl Cl  Cl H  Ni 2 Hexamethylenediamine                                                                        93.6%                                                                             yellow                78  H  H  H  H  H   H  H   H  CH.sub.3                                                                         Ni 2 Hexamethylenediamine                                                                        94.7%                                                                             yellow                79  H  H  H  H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni 2 Piperazine    82.1%                                                                             yellow                80  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 2 Piperazine    71.4%                                                                             yellow                81  H  H  H  H  Cl  Cl Cl  Cl H  Ni 2 Piperazine    35.3%                                                                             yellow                82  H  H  CH.sub.3                                                                         H  Cl  Cl Cl  Cl H  Ni 2 Piperazine    94.3%                                                                             yellow                83  H  H  CH.sub.3                                                                         H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni 2 Piperazine    65.5%                                                                             yellow                84  H  H  Cl H  Cl  Cl Cl  Cl H  Ni 2 Piperazine    78.2%                                                                             yellow                85  H  H  H  H  H   H  H   H  CH Ni 2 Piperazine    90.9%                                                                             yellow                86  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 2 p-Phenylenenediamine                                                                        98.3%                                                                             yellow                87  H  H  H  H  Cl  Cl CH.sub.3 O                                                                        Cl H  Ni 2 4,4'-Diamino-                                                                 diphenylsulphone                        88  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 2 Terephthaldialdehyde                                                                        96.7%                                                                             yellow                                                      bis-hydrazone                           89  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 2 Terephthalic acid                                                                           100%                                                                              yellow-brown                                                bis-hydrazide                           90  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 2 2-Methyl-4,4'-                                                                              94.7%                                                                             yellow                                                      Diaminobenzene                          91  H  H  H  H  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl H  Ni 3                                                                               87.5%         yellow                    92  H  H  H  H  Cl  Cl Cl  Cl C.sub.6 H.sub.5                                                                  Ni   Ethylenediamine   reddish-                                                                      tinged                                                                        yellow                __________________________________________________________________________

The metal complexes of the formula (B) wherein the symbols have themeaning indicated in Table 3, are obtained in accordance with theinstructions of Example 2. ##STR29##

The metal complexes of the formula (C) wherein the symbols have themeaning indicated in Table 4, are obtained in accordance with theinstructions of Example 2 if 4-hydroxycoumarin3-aldhyde is used insteadof 2,4-dihydroxyquinolinealdehyde. ##STR30##

                                      TABLE 3                                     __________________________________________________________________________    Ex-                                                                           ample                                                                             X.sub.3                                                                           X.sub.4                                                                           X.sub.5                                                                           X.sub.6                                                                           R    M   n      L            Yield                                                                               Shade                  __________________________________________________________________________     93 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  1   Aniline         89%  yellow                   94 Cl  Cl  OCH.sub.3                                                                         Cl  Phenyl                                                                             Ni  1   Aniline         89%  yellow                   95 OCH.sub.3                                                                         Cl  OCH.sub.3                                                                         Cl  Phenyl                                                                             Ni  1   Aniline         84%  yellow                   96 OCH.sub.3                                                                         Cl  OCH.sub.3                                                                         Cl  Phenyl                                                                             Ni  1   n-Octylamine    81%  yellow                   97 Cl  Cl  Cl  Cl  p-Tolyl                                                                            Ni  1   Aniline         85%  yellow                   98 Cl  Cl  OCH.sub.3                                                                         Cl  p-Tolyl                                                                            Ni  1   Aniline         85%  yellow                   99 OCH.sub.3                                                                         Cl  OCH.sub.3                                                                         Cl  p-Tolyl                                                                            Ni  1   n-Octylamine    87%  yellow                  100 Cl  Cl  Cl  Cl  H    Ni  1   NH.sub.3        98.1%                                                                              yellow                  101 Cl  Cl  Cl  Cl  OH   Ni  1   NH.sub.3        71.0%                                                                              yellow                  102 Cl  Cl  Cl  Cl  OH   Cu  1   NH.sub.3        92.3%                                                                              yellow                  103 CH.sub.3 O                                                                        Cl  CH.sub.3 O                                                                        Cl  OH   Ni  1   NH.sub.3        92.0%                                                                              yellow                  104 CH.sub.3 O                                                                        Cl  CH.sub.3 O                                                                        Cl  OH   Cu  1   NH.sub.3        96.0%                                                                              greenish-tinged                                                               yellow                  105 Cl  Cl  PhO Cl  OH   Ni  1   NH.sub.3        89.3%                                                                              yellow                  106 Cl  Cl  Cl  Cl  Ph   Ni  1   NH.sub.3        95.2%                                                                              yellow                  107 Cl  Cl  CH.sub.3 O                                                                        Cl  Ph   Ni  1   NH.sub.3        92.4%                                                                              yellow                  108 Cl  Cl  CH.sub.3 O                                                                        Cl  p-Tolyl                                                                            Ni  1   NH.sub.3        96.6%                                                                              yellow                  109 Cl  Cl  CH.sub.3 O                                                                        Cl  Ph   Ni  1   Benzylamine     93.9%                                                                              yellow                  110 Cl  Cl  CH.sub.3 O                                                                        Cl  p-Tolyl                                                                            Ni  1   Benzylamine     85.3%                                                                              yellow                  111 Cl  Cl  CH.sub.3 O                                                                        Cl  p-Tolyl                                                                            Ni  1   NH.sub.2CHNH    92.4%                                                                              yellow                  112 Cl  Cl  CH.sub.3 O                                                                        Cl  Phenyl                                                                             Ni  1   Pyridine        93.4%                                                                              yellow                  113 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  1   Pyridine        98.5%                                                                              yellow                  114 Cl  Cl  CH.sub.3 O                                                                        Cl  Phenyl                                                                             Cu  1   Aniline         87.5%                                                                              greenish-tinged                                                               yellow                  115 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  1   Benzylamine     97.0%                                                                              yellow-orange           116 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  1   Morpholine      98.1%                                                                              yellow                  117 Cl  Cl  Cl  Cl  OH   Ni  1   Benzylamine     85.4%                                                                              yellow                  118 Cl  Cl  Cl  Cl  OH   Ni  1   Aniline         78.4%                                                                              yellow                  119 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  1   N-Methylpiperazine                                                                            91.7%                                                                              yellow                  120 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  1   N-Phenylpiperazine                                                                            97.8%                                                                              yellow                  121 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  1   2-Aminobenzimidazole                                                                          94.6%                                                                              brown                   122 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  1   Hydrazine hydrate                                                                             99.5%                                                                              yellow                  123 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  1   2-Aminobenzthiazole                                                                           87.6%                                                                              yellow-brown            124 CH.sub.3 O                                                                        Cl  CH.sub.3 O                                                                        Cl  Phenyl                                                                             Ni  1   Benzylamine     83.3%                                                                              yellow                  125 Cl  Cl  Cl  Cl  OH   Ni  2   Ethylenediamine 70.9%                                                                              yellow                  126 Cl  Cl  CH.sub.3 O                                                                        Cl  OH   Ni  2   Ethylenediamine 92.3%                                                                              yellow                  127 CH.sub.3 O                                                                        Cl  CH.sub.3 O                                                                        Cl  OH   Ni  2   Ethylenediamine 84.6%                                                                              yellow                  128 Cl  Cl  Cl  Cl  H    Ni  2   Ethylenediamine 87.9%                                                                              yellow                  129 Cl  Cl  CH.sub.3 O                                                                        Cl  Phenyl                                                                             Ni  2   Ethylenediamine 93.1%                                                                              yellow                  130 Cl  Cl  CH.sub.3 O                                                                        Cl  p-Tolyl                                                                            Ni  2   Ethylenediamine 90.1%                                                                              yellow                  131 Cl  Cl  Cl  Cl  OH   Ni  2   Propylenediamine                                                                              82.5%                                                                              yellow                  132 Cl  Cl  Cl  Cl  OH   Ni  2   Piperazine      93.5%                                                                              yellow                  133 Cl  Cl  Cl  Cl  H    Ni  2   Piperazine      96.0%                                                                              yellow                  134 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  2   Piperazine      100% yellow                  135 Cl  Cl  CH.sub.3 O                                                                        Cl  Phenyl                                                                             Ni  2   Piperazine      86.6%                                                                              yellow                  136 Cl  Cl  CH.sub.3 O                                                                        Cl  p-Tolyl                                                                            Ni  2   Piperazine      93.3%                                                                              yellow                  137 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  2   4,4'-Diaminodiphenylsulphone                                                                  88.2%                                                                              yellow                  138 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  2   4,4' -Diaminocyclohexane                                                                      95.8%                                                                              yellow                  139 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  2   2-Methyl-4,4'-diamino-                                                                        89.9%                                                                              yellow                                                   azobenzene                                   140 Cl  Cl  Cl  Cl  Phenyl                                                                             Ni  2   1,3-Diphenyldiaminopropane                                                                    90.1%                                                                              yellow                  141 CH.sub.3 O                                                                        Cl  CH.sub.3 O                                                                        Cl  Phenyl                                                                             Ni  2   Piperazine           yellow                  142 CH.sub.3 O                                                                        Cl  CH.sub.3 O                                                                        Cl  p-Tolyl                                                                            Ni  2   Piperazine           yellow                  143 CH.sub.3 O                                                                        Cl  CH.sub.3 O                                                                        Cl  Phenyl                                                                             Ni  2   Ethylenediamine      yellow                  144 CH.sub.3 O                                                                        Cl  CH.sub.3 O                                                                        Cl  Phenyl                                                                             Ni  2   Ethylenediamine      yellow                  __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    Ex-                                                 Shade in                  ample                                                                             Y.sub.1                                                                          Y.sub.2                                                                           Y.sub.3                                                                           Y.sub.4                                                                           X.sub.3                                                                          X.sub.4                                                                          X.sub.5                                                                           X.sub.6                                                                          M n      L     Yield                                                                              PVC                       __________________________________________________________________________    145 H  H   H   H   Cl Cl Cl  Cl Ni                                                                              1 NH.sub.3   98.2%                                                                              yellow                    146 H  H   H   H   Cl Cl CH.sub.3 O                                                                        Cl Ni                                                                              1 NH.sub.3   100% yellow                    147 H  H   CH.sub.3                                                                          H   Cl Cl Cl  Cl Ni                                                                              1 NH.sub.3   94.4%                                                                              yellow                    148 H  H   CH.sub.3                                                                          H   Cl Cl CH.sub.3 O                                                                        Cl Ni                                                                              1 NH.sub.3   85.7%                                                                              yellow                    149 H  H   Cl  H   Cl Cl Cl  Cl Ni                                                                              1 NH.sub.3   98.5%                                                                              yellow                    150 H  H   Cl  H   Cl Cl CH.sub.3 O                                                                        Cl Ni                                                                              1 NH.sub.3   82.4%                                                                              yellow                    151 H  CH.sub.3                                                                          Cl  CH.sub.3                                                                          Cl Cl Cl  Cl Ni                                                                              1 NH.sub.3   85.0%                                                                              yellow                    152 H  H   H   H   Cl Cl Cl  Cl Ni                                                                              1 NH.sub.3   97.6%                                                                              yellow                    153 H  H   H   H   Cl Cl CH.sub.3 O                                                                        Cl Ni                                                                              1 NH.sub.3   87.5%                                                                              yellow                    154 H  H   CH.sub.3                                                                          H   Cl Cl Cl  Cl Ni                                                                              1 NH.sub.3   97.1%                                                                              yellow                    155 H  H   CH.sub.3                                                                          H   Cl Cl CH.sub.3 O                                                                        Cl Ni                                                                              1 NH.sub.3   90.6%                                                                              yellow                    156 H  H   Cl  H   Cl Cl Cl  Cl Ni                                                                              1 Benzylamine                                                                              94.1%                                                                              yellow                    157 H  H   Cl  H   Cl Cl CH.sub.3 O                                                                        Cl Ni                                                                              1 Benzylamine                                                                              90.0%                                                                              yellow                    158 H  CH.sub.3                                                                          Cl  CH.sub.3                                                                          Cl Cl Cl  Cl Ni                                                                              1 Benzylamine                                                                              87.5%                                                                              yellow                    159 H  H   CH.sub.3                                                                          H   Cl Cl Cl  Cl Ni                                                                              1 Benzylamine                                                                              89.7%                                                                              yellow                    160 H  H   Cl  H   Cl Cl Cl  Cl Ni                                                                              1 Benzylamine                                                                              98.3%                                                                              yellow                    161 H  H   H   H   Cl Cl Cl  Cl Ni                                                                              1 Pyridine   99.2%                                                                              yellow                    162 H  H   CH.sub.3                                                                          H   Cl Cl Cl  Cl Ni                                                                              1 Pyridine   94.5%                                                                              yellow                    163 H  H   Cl  H   Cl Cl Cl  Cl Ni                                                                              1 Pyridine   93.6%                                                                              yellow                    164 H  H   H   H   Cl Cl Cl  Cl Ni                                                                              1 Morpholine 92.9%                                                                              yellow                    165 H  H   H   H   Cl Cl Cl  Cl Ni                                                                              2 Ethylenediamine                                                                          94.0%                                                                              yellow                    166 H  H   H   H   Cl Cl CH.sub.3 O                                                                        Cl Ni                                                                              2 Ethylenediamine                                                                          85.7%                                                                              yellow                    167 H  H   CH.sub.3                                                                          H   Cl Cl Cl  Cl Ni                                                                              2 Ethylenediamine                                                                          96.5%                                                                              yellow                    168 H  H   CH.sub.3                                                                          H   Cl Cl CH.sub.3 O                                                                        Cl Ni                                                                              2 Ethylenediamine                                                                          92.9%                                                                              yellow                    169 H  H   Cl  H   Cl Cl Cl  Cl Ni                                                                              2 Ethylenediamine                                                                          89.2%                                                                              yellow                    170 H  CH.sub.3                                                                          Cl  CH.sub.3                                                                          Cl Cl Cl  Cl Ni                                                                              2 Ethylenediamine                                                                          78.4%                                                                              yellow                    171 H  H   H   H   Cl Cl Cl  Cl Ni                                                                              2 Ethylenediamine                                                                          91.0%                                                                              yellow                    172 H  H   H   H   Cl Cl Cl  Cl Ni                                                                              2 Hexamethylenediamine                                                                     86.3%                                                                              yellow                    173 H  H   H   H   Cl Cl Cl  Cl Ni                                                                              2 Triethylenediamine                                                                       93.0%                                                                              yellow                    174 H  H   H   H   Cl Cl Cl  Cl Ni                                                                              2 Piperazine 94.7%                                                                              yellow                    175 H  H   H   H   Cl Cl CH.sub.3 O                                                                        Cl Ni                                                                              2 Piperazine 82.1%                                                                              yellow                    176 H  H   CH.sub.3                                                                          H   Cl Cl CH.sub.3 O                                                                        Cl Ni                                                                              2 Piperazine 89.7%                                                                              yellow                    177 H  H   Cl  H   Cl Cl Cl  Cl Ni                                                                              2 Piperazine 89.6%                                                                              yellow                    178 H  H   H   H   Cl Cl Cl  Cl Ni                                                                              2 4,4'-Diamino-                                                                            71.5%                                                                              yellow                                                        diphenylsulphone                          __________________________________________________________________________

The metal complexes of the formula (D) in Table 5 were synthesised asdescribed in Example 2. ##STR31##

                                      TABLE 5                                     __________________________________________________________________________    Example                                                                            X.sub.3                                                                          X.sub.4                                                                          X.sub.5                                                                           X.sub.6                                                                          R M n    L     Yield                                                                              Shade in PVC                            __________________________________________________________________________    179  Cl Cl Cl  Cl H Ni                                                                              1 NH.sub.3 91.6%                                                                              orange                                  180  Cl Cl CH.sub.3 O                                                                        Cl H Ni                                                                              1 NH.sub.3 100% yellow-orange                           181  Cl Cl Cl  Cl H Ni                                                                              1 Benzylamine                                                                            94.5%                                                                              orange                                  182  Cl Cl CH.sub.3 O                                                                        Cl H Ni                                                                              1 Benzylamine                                                                            100% orange                                  183  Cl Cl Cl  Cl H Ni                                                                              1 Aniline  92.0%                                                                              brown                                   184  Cl Cl Cl  Cl H Ni                                                                              1 Pyridine 97.4%                                                                              brown                                   185  Cl Cl CH.sub.3 O                                                                        Cl H Ni                                                                              2 Ethylenediamine                                                                        96.4%                                                                              orange                                  __________________________________________________________________________

The metal complexes of the formula (E) wherein the symbols have themeaning indicated in Table 6, are obtained in accordance with theinstructions of Example 2. ##STR32##

                                      TABLE 6                                     __________________________________________________________________________    Example                                                                            X.sub.3                                                                           X.sub.4                                                                          X.sub.5                                                                           X.sub.6                                                                          M n    L     Yield                                                                              Shade in PVC                             __________________________________________________________________________    186  H   H  H   H  Ni                                                                              1 NH.sub.3 78.6%                                                                              yellow                                   187  CH.sub.3 O                                                                        Cl CH.sub. 3 O                                                                       Cl Ni                                                                              1 NH.sub.3 90.0%                                                                              yellow                                   188  Cl  Cl Cl  Cl Ni                                                                              2 Ethylenediamine                                                                        88.0%                                                                              yellow                                   189  H   H  H   H  Ni                                                                              2 Ethylenediamine                                                                        85.7%                                                                              yellow                                   190  Cl  Cl CH.sub.3 O                                                                        Cl Ni                                                                              2 Ethylenediamine                                                                        87.1%                                                                              yellow                                   191  CH.sub.3 O                                                                        H  CH.sub.3 O                                                                        Cl Ni                                                                              2 Ethylenediamine                                                                        87.1%                                                                              yellow                                   192  H   H  H   H  Ni                                                                              2 Piperazine                                                                             66.7%                                                                              yellow                                   193  Cl  Cl CH.sub.3 O                                                                        Cl Ni                                                                              2 Piperazine                                                                             54.8%                                                                              yellow                                   194  CH.sub.3 O                                                                        Cl CH.sub.3 O                                                                        Cl Ni                                                                              2 Piperazine                                                                             83.9%                                                                              yellow                                   __________________________________________________________________________

Metal complexes of the formula (F) wherein the symbols have the meaningindicated in Table 7, are obtained in accordance with instructions ofExample 2. ##STR33##

                                      TABLE 7                                     __________________________________________________________________________    Example                                                                             X.sub.3                                                                            X.sub.4                                                                          X.sub.5                                                                            X.sub.6                                                                          M  n     L     Yield                                                                              Shade in PVC                        __________________________________________________________________________    195   Cl   Cl Cl   Cl Ni 1  NH.sub.3 88.5%                                                                              yellow                              196   Cl   Cl CH.sub.3                                                                           Cl Ni 1  NH.sub.3 92.6%                                                                              yellow                              197   Cl   Cl CH.sub.3 O                                                                         Cl Ni 1  Benzylamine                                                                            84.4%                                                                              yellow                              198   Cl   Cl Cl   Cl Ni 1  Benzylamine                                                                            71.9%                                                                              yellow                              199   Cl   Cl Cl   Cl Ni 1  Aniline  90.0%                                                                              yellow                              200   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl Ni 1  Aniline  86.5%                                                                              yellow                              201   Cl   Cl Cl   Cl Ni 1  Pyridine 93.5%                                                                              yellow                              202   Cl   Cl Cl   Cl Ni 2  Ethylenediamine                                                                        80.1%                                                                              yellow                              203   Cl   Cl CH.sub.3 O                                                                         Cl Ni 2  Ethylenediamine                                                                        85.7%                                                                              yellow                              204   Cl   Cl Cl   Cl Ni 2  4,4'-diamino-                                                                          74.0%                                                                              yellow                                                          diphenylsulphone                                  __________________________________________________________________________

The metal complexes of the formula (G) wherein the symbols have themeaning indicated in Table 8, are obtained in accordance with theinstructions of Example 2. ##STR34##

                                      TABLE 8                                     __________________________________________________________________________    Ex-                                                     Shade in              ample                                                                              X.sub.3                                                                            X.sub.4                                                                           X.sub.5                                                                            X.sub.6                                                                             R        M   n    L       Yield                                                                              PVC                   __________________________________________________________________________    205  Cl   Cl  Cl   Cl  H          Ni  1  NH.sub.3  92.0%                                                                              red                   206  Cl   Cl  Cl   Cl  COOH       Ni  1  NH.sub.3  97.5%                                                                              orange                207  Cl   Cl  Cl   Cl                                                                                Ni         1   NH.sub.3                                                                         100%      orange                     208  Cl   Cl  Cl   Cl  H          Ni  1  Benzylamine                                                                             88.1%                                                                              orange                209  Cl   Cl  Cl   Cl                                                                                Ni#STR35##     Benzylamine                                                                      68.9%     orange                     210  Cl   Cl  Cl   Cl  H          Ni  1  Aniline   95.3%                                                                              brown                 211  CH.sub.3 O                                                                         Cl  CH.sub.3 O                                                                         Cl                                                                                Ni#STR36## 1   Aniline                                                                          78.4%     brown                      212  Cl   Cl  Cl   Cl  H          Ni  1  Pyridine  94.6%                                                                              red                   213  Cl   Cl  Cl   Cl                                                                                Ni#STR37## 1   Pyridine                                                                         94.7%     brown                      214  Cl   Cl  Cl   Cl  H          Ni  1  Morpholine                                                                              86.0%                                                                              red                   215  Cl   Cl  Cl   Cl                                                                                Ni#STR38## 1   Morpholine                                                                       93.1%     red                        216  Cl   Cl  Cl   Cl  H          Ni  1  N-methylpip-                                                                            79.4%                                                                              orange                                                         erazine                              217  Cl   Cl  Cl   Cl  H          Ni  1  N-phenylpip-                                                                            93.6%                                                                              red                                                            erazine                              218  Cl   Cl  Cl   Cl  H          Ni  2  Ethylene- 95.2%                                                                              red                                                            diamine                              219  Cl   Cl  CH.sub.3 O                                                                         Cl  H          Ni  2  Ethylene- 85.2%                                                                              orange                                                         diamine                              220  Cl   Cl  Cl   Cl                                                                                Ni#STR39## 2   Ethylene- diamine                                                                91.0%     red                        221  Cl   Cl  Cl   Cl                                                                                Ni#STR40## 2   Piperazine                                                                       99.0%     orange                     222  Cl   Cl  Cl   Cl  H          Ni  2  Piperazine                                                                              95.3%                                                                              red                   223  Cl   Cl  Cl   Cl  COOH       Ni  2  Piperazine                                                                              91.4%                                                                              red-brown             224  Cl   Cl  Cl   Cl  H          Ni  2  4,4'-diamino-                                                                           88.8%                                                                              orange                                                         diphenylsulphone                     225  Cl   Cl  Cl   Cl  COOH       Ni  2  1,4-diamino-                                                                            70.5%                                                                              red-brown                                                      cyclohexane                          __________________________________________________________________________

Metal complexes of the formula (H) wherein the symbols have the meaningindicated in Table 9, are obtained in accordance with the instructionsof Example 2. ##STR41##

                                      TABLE 9                                     __________________________________________________________________________    Example                                                                          X.sub.3                                                                             X.sub.4                                                                          X.sub.5                                                                            X.sub.6                                                                          R.sub.1                                                                          R.sub.2                                                                          M  n     L      Yield                                                                              Shade in                       __________________________________________________________________________                                                   PVC                            226   Cl Cl Cl   Cl H  H  Ni 1  NH.sub.3  98.7%                                                                              organge                        227   Cl Cl CH.sub.3 O                                                                         Cl Cl Cl Ni 1  NH.sub.3  96.3%                                                                              red-brown                      228   Cl Cl Cl   Cl Cl Cl Ni 1  Benzylamine                                                                             92.0%                                                                              orange                         229   Cl Cl Cl   Cl Cl Cl Ni 1  Aniline   91.7%                                                                              yellow-orange                  230   Cl Cl Cl   Cl Cl Cl Ni 1  Pyridine  100% yellow-orange                  231   Cl Cl Cl   Cl Cl Cl Ni 1  Morpholine                                                                              95.4%                                                                              orange                         232   Cl Cl Cl   Cl H  H  Ni 1  Morpholine                                                                              91.3%                                                                              yellow-orange                  233   Cl Cl Cl   Cl Cl Cl Ni 2  Ethylenediamine                                                                         86.7%                                                                              red-brown                      234   Cl Cl Cl   Cl Cl Cl Ni 2  Ethylenediamine                                                                         71.4%                                                                              red-brown                      235   Cl Cl Cl   Cl Cl Cl Ni 2  Piperazine                                                                              99.3%                                                                              red-brown                      236   Cl Cl Cl   Cl H  H  Ni 2  Piperazine                                                                              94.0%                                                                              yellow-orange                  237   Cl Cl Cl   Cl Cl Cl Ni 2  4,4'-Diamino-                                                                           98.3%                                                                              yellow                                                         diphenylsulphone                              __________________________________________________________________________

The metal complexes of the formula (I) wherein the symbols have themeaning indicated in Table 10, are obtained in accordance with theinstructions of Example 2. ##STR42##

                                      TABLE 10                                    __________________________________________________________________________                                                 Shade in                         Example                                                                             X.sub.3                                                                          X.sub.4                                                                          X.sub.5                                                                            X.sub.6                                                                           R   M  n     L     Yield                                                                               PVC                             __________________________________________________________________________    238   Cl Cl Cl   Cl CH.sub.3                                                                           Ni 1  NH.sub.3 81.9%                                                                              yellow                           239   Cl Cl CH.sub.3 O                                                                         Cl CONH.sub.2                                                                         Ni 1  NH.sub.3 91.3%                                                                              yellow                           240   Cl Cl CH.sub.3 O                                                                         Cl CONH.sub.2                                                                         Ni 1  Benzylamine                                                                            77.8%                                                                              yellow                           241   Cl Cl Cl   Cl CH.sub.3                                                                           Ni 1  Aniline  82.8%                                                                              yellow                           242   Cl Cl Cl   Cl CH.sub.3                                                                           Ni 2  Ethylenediamine                                                                        84.1%                                                                              yellow                           243   Cl Cl CH.sub.3 O                                                                         Cl CONH.sub.2                                                                         Ni 2  Ethylenediamine                                                                        90.0%                                                                              yellow                           __________________________________________________________________________

The metal complexes of the formula (J) wherein the symbols have themeaning indicated in Table 11, are obtained in accordance with theinstructions of Example 2. ##STR43##

                                      TABLE 11                                    __________________________________________________________________________    Ex- ample                                                                          X.sub.3                                                                           X.sub.4                                                                           X.sub.5                                                                           X.sub.6                                                                           M                                                                                 n                L                                                                              Yield    Shade                     __________________________________________________________________________                                                        in PVC                    244  Cl  Cl  Cl  Cl  Ni                                                                                1##STR44##    NH.sub.3                                                                          91.7%    red                       245  Cl  Cl  Cl  Cl  Ni  "             1   Benzylamine                                                                            84.5%                                                                              orange               246  Cl  Cl  Cl  Cl  Ni  "             1   Pyridine 92.0%                                                                              orange               247  Cl  Cl  Cl  Cl  Ni  "             2   Ethylenediamine                                                                        90.5%                                                                              orange               248  Cl  Cl  Cl  Cl  Ni                                                                                1##STR45##    NH.sub.3                                                                          96.9%    yellow                    249  Cl  Cl  Cl  Cl  Ni  "             2   Piperazine                                                                             96.0%                                                                              orange               250  Cl  Cl  Cl  Cl  Ni                                                                                1##STR46##    NH.sub.3                                                                          54.6%    yellow                    251  Cl  Cl  Cl  Cl  Ni  "             1   Benzylamine                                                                            71.4%                                                                              yellow               252  Cl  Cl  Cl  Cl  Ni  "             1   Aniline  71.8%                                                                              yellow               253  Cl  Cl  Cl  Cl  Ni  "             1   Pyridine 88.5%                                                                              yellow               254  Cl  Cl  Cl  Cl  Ni                                                                                2##STR47##    Ethylenediamine                                                                   94.6%    yellow                    255  Cl  Cl  Cl  Cl  Ni  "             2   Piperazine                                                                             96.0%                                                                              yellow               256  Cl  Cl  Cl  Cl  Ni                                                                                2##STR48##    Piperazine                                                                        92.5%    yellow                    257  Cl  Cl  Cl  Cl  Ni  "             2   Ethylenediamine                                                                        89.8%                                                                              yellow               258  Cl  Cl  Cl  Cl  Ni  "             1   NH.sub.3 93.8%                                                                              yellow               __________________________________________________________________________

EXAMPLE 259

189 parts of 2,4-dihydroxyquinoline-3-aldehyde and 2.99 parts of4,5,6,7-tetrachloroisoindolin-1-onylidenehydrazine are stirred for 15minutes at 100° C in 150 parts by volume of methylcellosolve. Afteradding 0.93 part of aniline, followed by 2.50 parts of nickel acetatetetrahydrate, the yellow suspension is stirred for a further 4 hours at100° C. The reaction product is then filtered off while hot, washed wellwith methylcellosolve, alcohol and acetone and dried at 80° C in vacuo.This gives 6.0 parts (97% of theory) of an analytically pure, yellowpigment having the formula indicated in Example 1.

For those examples in which L denotes NH₃, a gentle stream of ammonia ispassed in during the metallisation.

Half a mol of diamine was used for the examples in which n denotes 2,and a third of a mol of triamine was used for Example 91.

EXAMPLE 260

2 g of the pigment prepared in accordance with Example 1 are ground on atriple roll mill together with 36 g of hydrated alumina, 60 g of linseedoil varnish of medium viscosity and 2 g of cobalt linoleate. The yellowprints produced using the resulting colorant paste are deep andoutstandingly fast to light.

EXAMPLE 261

0.6 g of the pigment prepared in accordance with Example 1 is mixed with67 g of polyvinyl chloride, 33 g of dioctyl phthalate, 2 g ofdibutyl-tin dilaurate and 2 g of titanium dioxide and the mixture isprocessed on a roll mill for 15 minutes at 160° C to give a thin sheet.The yellow coloration thus produced is deep and fast to migration, heatand light.

EXAMPLE 262

10 g of titanium dioxide and 2 g of the pigment prepared in accordancewith Example 2 are ground for 48 hours in a ball mill together with 88 gof a mixture of 26.4 g of coconut alkyd resin, 24.0 g ofmelamine-formaldehyde resin (50% solids content), 8.8 g of ethyleneglycol monomethyl ether and 28.8 g of xylene.

If this lacquer is sprayed onto an aluminium foil, predried for 30minutes at room temperature and then stoved for 30 minutes at 120° C, ayellow lacquering is obtained, which is distinguished by good depth ofcolour and by very good fastness to overlacquering, ligth andweathering.

We claim:
 1. A bis-hydrazone metal complex of the formula ##STR49##wherein A denotes ##STR50## wherein M denotes a divalent transitionmetal, zinc or cadmium, Y₁ and Y₂ denote hydrogen, halogen, alkyl of 1-4carbon atoms, alkoxy of 1-4 carbon atoms, or nitro; Z denotes --NH-- or-oxygen-, R₈ denotes -OH, alkyl containing 1-4 carbon atoms, phenyl,phenyl substituted with halogen, alkyl of 1-4 carbon atoms, or alkoxy of1-4 carbon atoms; R₉ denotes cyano, carboxyl, or carbamoyl; R₁₀ denoteshydrogen, or alkyl; Y₃ denotes hydrogen, carboxyl, carbamoyl,phenylcarbamoyl or alkoxycarbonyl containing 2-6 carbon atoms; Y₄denotes hydrogen, halogen, methoxy, nitro or cyano; R₁₁ denotes alkyl of1-4 carbon atoms, alkoxycarbonyl containing 2-5 carbon atoms, carboxyl,carbamoly, ##EQU2## wherein M₂ denotes Ca, Sr, Ba or Mn; L denotes##STR51## wherein R' denotes hydrogen, hydroxyl, alkyl having 1-10carbon atoms, phenalkyl containing 1-4 carbon atoms, cycloalkylcontaining 5-6 carbon atoms, an aromatic group selected from the groupconsisting of phenyl, methylphenyl, chlorophenyl, or methoxyphenyl,amino, alkylamino containing 1-6 carbon atoms, or a group of theformulas ##STR52## wherein R₂ and R₃ denote hydrogen, alkyl of 1-6carbon atoms, or phenyl; R'" denotes hydrogen, amino, alkyl containing1-6 carbon atoms, phenyl, phenyl substituted by halogen, alkylcontaining 1-4 carbon atoms or alkoxy containing 1-4 carbon atoms; Rdenotes hydrogen, alkyl containing 1-4 carbon atoms or phenyl; B denotesa radical which, conjointly with the N atoms, forms a heterocyclic ringselected from the group consisting of pyridine, quinoline, piperidine,or morpholine; B₁ denotes alkylene containing 2-10 carbon atoms,phenylene, a group --Ph--X--Ph-- wherein X denotes a direct bond, --O--,--S--, methylene, ethylene, -NH-, --SO₂ --, --CO-- or --N=N--; X₃denotes hydrogen, halogen, alkoxy containing 1-6 carbon atoms, nitro,carboxyl, carbamoyl, or alkanolyamino containing 2-6 carbon atoms; X₄denotes hydrogen or chloro; X₅ denotes hydrogen, chloro, alkoxy,containing 1-6 carbon atoms, alkylmercapto containing 1-6 carbon atoms,phenalkoxy having an alkyl containing 1-4 carbon atoms or phenoxy; X₆denotes hydrogen, chloro, nitro, carboxyl, carbamoyl, alkylcarbamoylcontaining 2-6 carbon atoms, alkanoylamino containing 2-6 carbon atomsor phenylcarbamoyl; and m denotes the number 1-2.
 2. A bis-hydrazonemetal complex according to claim 1 of the formula ##STR53## wherein A,R, M and X₃ - X₆ have the meaning indicated in claim 1, and B₁ denotesan alkylene group containing 2 - 10 C atoms, or a phenylene group.
 3. Abis-hydrazone metal complex according to claim 1, wherein, in theformulae indicated, R denotes a H atom, an alkyl group containing 1 - 4C atoms, or a phenyl group.
 4. A bis-hydrazone metal complex accordingto claim 1, wherein M denotes a copper atom or, a Ni atom.
 5. Abis-hyrazone metal complex according to claim 1, wherein X₄ and X₆denote H or chlorine atoms, and X₃ and X₅ denote H or chlorine atoms oralkoxy groups containing 1 - 4 C atoms.
 6. A bis-hydrazone metal complexaccording to claim 1, wherein A denotes a radical of the formula##STR54## wherein Y₁ Y₂ denote H or halogen atoms, alkyl or alkoxygroups containing 1 - 4 C atoms, or nitro groups.
 7. A bis-hydrazonemetal complex according to claim 1, wherein A denotes a radical of theformula ##STR55## wherein R₈ denotes an OH group, an alkyl groupcontaining 1 - 4 C atoms, or a phenyl radical which is optionallysubstituted by halogen atoms or alkyl or alkoxy groups containing 1 - 4C atoms.
 8. A bis-hydrazone metal complex according to claim 1, whereinA denotes a radical of the formula ##STR56## wherein Y₁ and Y₂ have themeaning indicated in claim
 1. 9. A bis-hydrazone metal complex accordingto claim 1, wherein L denotes ammonia.
 10. A bis-hydrazone metal complexaccording to claim 1, wherein L denotes ethylenediamine.
 11. Abis-hydrazone metal complex according to claim 1, wherein L denotespiperazine.
 12. The compound as claimed in claim 1 of the formula##STR57##
 13. The compound as claimed in claim 1 of the formula##STR58##
 14. The compound as claimed in claim 1 of the formula##STR59##
 15. The compound as claimed in claim 1 of the formula##STR60##
 16. The compound as claimed in claim 1 of the formula##STR61##